EP0133739B1 - Process for preparing 2-alkyl-1,4-butanediols - Google Patents
Process for preparing 2-alkyl-1,4-butanediols Download PDFInfo
- Publication number
- EP0133739B1 EP0133739B1 EP84303842A EP84303842A EP0133739B1 EP 0133739 B1 EP0133739 B1 EP 0133739B1 EP 84303842 A EP84303842 A EP 84303842A EP 84303842 A EP84303842 A EP 84303842A EP 0133739 B1 EP0133739 B1 EP 0133739B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- butanediol
- mixture
- alkyl
- preparing
- butynediol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
Definitions
- This invention relates to a process for the preparation of 2 - alkyl - 1,4 - butanediols. It is more particularly directed to a process for preparing such butanediols from 1,4 - butynediol or 1,4 - butenediol by catalytic hydrogenation and reaction with an aldehyde.
- the 2 - alkyl - 1,4 - butanediols are a useful class of compounds in that they can be cyclized to the corresponding 3 - alkyltetrahydrofurans, which in turn can be copolymerized with tetrahydrofuran to form polyethers useful in preparing polyurethane elastomers.
- 2 - alkylbutanediols can be prepared from 1,4 - butynediol or 1,4 - butenediol by catalytic hydrogenation and reaction with an aldehyde. It is believed that the process proceeds according to the equations where R is hydrogen or an alkyl radical of 1-4 carbon atoms.
- reaction is conveniently conducted by bringing together, at a pH of about 9--12, and at a temperature and pressure suitable for reaction, the butynediol or butenediol, hydrogen, an appropriate aldehyde, and a suitable hydrogenation catalyst.
- the process may be run by itself, but it has been found, surprisingly, that it can also be run simultaneously with and in the same reaction vessel as the process shown in British Patent 1,242,358, according to which 1,4 - butanediol is produced from 1,4 - butynediol by catalytic hydrogenation using Raney nickel as the catalyst.
- the process produces a mixture of 1,4-butanediol and a 2 - alkyl - 1,4 - butanediol. While these can be easily separated by conventional procedures, it may be desirable to keep the mixture intact for it can be cyclized in one step to give a mixture of tetrahydrofuran and a 3 - alkyltetrahydrofuran.
- a tetrahydrofuran/3 - alkyltetrahydrofuran copolymer can then be prepared directly from this mixture by adding a suitable catalyst and holding the mixture under conditions suitable for copolymerization.
- the process of the invention can be run batchwise, but is more conveniently and preferably run continuously.
- a column reactor of appropriate dimensions is packed in the usual manner with a conventional hydrogenation catalyst.
- Suitable catalysts are, for example, platinum, Raney nickel and cobalt. Raney nickel, especially Raney nickel from which about 25% by weight of aluminum has been removed, is preferred.
- the catalyst may be in any convenient form, but is ordinarily and preferably granular.
- the butynediol used may be any commercially available type, and may be, for example, that obtained by catalytically reacting acetylene and formaldehyde, using a copper acetylide complex as the catalyst, as described in U.S. Patent 3,560,576 to Kirchner.
- the butenediol if that is used as a starting material, can likewise be of any commercially available type, and may be, for example, that obtained by the conventional hydrogenation of butynediol.
- the pH value of the butynediol or butenediol is adjusted to the range 8-14, preferably about 10-11, and is then fed continuously through the reaction column.
- the aldehyde ordinarily as an aqueous solution, is also fed continuously through the column.
- the aldehyde will be one having the structure shown in equation (1), and will preferably be formaldehyde.
- Enough aldehyde. is fed into the column to provide a diol/aldehyde weight ratio of 2/1 to 200/1, preferably 10/1 to 25/1.
- butynediol is obtained by the previously mentioned Kirchner method, it may already contain the proper amount of formaldehyde as an impurity, and separate addition of formaldehyde to the column may be unnecessary.
- Hydrogen is continuously fed into the column, in co-current or countercurrent flow to the other reactants, and is conveniently maintained in the column at a pressure of 6895-55160 kPa (gauge), preferably 34475 kPa (gauge).
- the exit temperature of the reaction mass conveniently is maintained at 10o-200°C, preferably about 140°-150°, by recycling according to well known chemical engineering principles.
- Flow of reactants into the reactor is conveniently regulated to give them a residence time in the reactor of 30-200 minutes, preferably 100-120 minutes.
- the 2 - alkylbutanediol is removed from the column in liquid form, as a mixture with 1,4 - butanediol.
- the alkylbutandiol can be separated from the 1,4 - butanediol, if one wishes to do this, by fractional distillation conducted according to well known chemical engineering principles.
- the process of the invention when run in the batch mode, is conducted under basically the same conditions, using the proportions of reactants and the recovery procedures just described.
- the 2 - alkylbutanediol produced may be catalytically cyclized to a corresponding 3 - alkyltetrahydrofuran, using sulfuric acid as the catalyst, by the general method disclosed in U.S. Patent 3,726,905 to Coates and Reilly. If the product, a mixture of 1,4 - butanediol and 2 - alkyl - 1,4 - butanediol, is kept intact as it comes from the reaction column, both components can be simultaneously cyclized using this method, to give a corresponding mixture of tetrahydrofuran and 3 - alkyltetrahydrofuran.
- This mixture can then be copolymerized to form a tetrahydrofuran/3 - alkyltetrahydrofuran copolymer using fluosulfonic acid as the catalyst, as disclosed in U.S. Patent 3,358,042 to Dunlop and Sherman.
- This copolymer can then be used to prepare a polyurethane by the general method disclosed in U.S. Patent 4,120,850 to Pechhold.
- 1,4 - Butynediol a 50% aqueous solution containing 0.4% of formaldehyde, prepared as shown in U.S. Patent 3,560,576, was brought to pH 11 with sodium hydroxide and then continuously fed into the bottom of the column at a rate of 9 ml per minute.
- Hydrogen was pumped into the bottom of the column and maintained in the column at a pressure of about 34475 kPa (gauge).
- the exit temperature of the product was maintained at about 140°C by recycling.
- the resulting slurry had a pH of 11-12.
- the slurry was heated to and held at 150°C and a hydrogen pressure of 34475 kPa (gauge), and shaken for one hour.
- the product was a mixture the organic portion of which was composed of 13.2% 2 - methyl - 1,4 - butanediol, 76.7% 1,4 - butanediol, and minor amounts of methanol and butanol.
- the resulting slurry had a pH of 11.9.
- the slurry was heated to and held at 140°C and a hydrogen pressure of 20,684 kPa (gauge) and shaken for 2 hours.
- the product was a mixture the organic portion of which was composed of 10.4% 2 - methyl - 1,4 - butanediol, 73.5% 1,4 - butanediol and minor amounts of methanol and butanol.
Description
- This invention relates to a process for the preparation of 2 - alkyl - 1,4 - butanediols. It is more particularly directed to a process for preparing such butanediols from 1,4 - butynediol or 1,4 - butenediol by catalytic hydrogenation and reaction with an aldehyde.
- The 2 - alkyl - 1,4 - butanediols, especially 2 - methyl - 1,4 - butanediol, are a useful class of compounds in that they can be cyclized to the corresponding 3 - alkyltetrahydrofurans, which in turn can be copolymerized with tetrahydrofuran to form polyethers useful in preparing polyurethane elastomers.
- In the past, these 2 - alkylbutanediols have been prepared by the reduction of itaconic acid, or by the hydroformylation and hydrogenation or 1,4 - butenediol described by Copelin in his U.S. Patent 3,859,369.
- It has now been found, according to the process of this invention, that 2 - alkylbutanediols can be prepared from 1,4 - butynediol or 1,4 - butenediol by catalytic hydrogenation and reaction with an aldehyde. It is believed that the process proceeds according to the equations
- When the starting material is butynediol (equation 1), intermediate butenediol is produced, which is further hydrogenated to the product 2 - alkyl - 1,4 - butanediol. The same product can also be made by using the butenediol as the starting material and omitting the step of equation 1 entirely.
- In either case the reaction is conveniently conducted by bringing together, at a pH of about 9--12, and at a temperature and pressure suitable for reaction, the butynediol or butenediol, hydrogen, an appropriate aldehyde, and a suitable hydrogenation catalyst.
- When butynediol is used as the starting material, the process may be run by itself, but it has been found, surprisingly, that it can also be run simultaneously with and in the same reaction vessel as the process shown in British Patent 1,242,358, according to which 1,4 - butanediol is produced from 1,4 - butynediol by catalytic hydrogenation using Raney nickel as the catalyst.
- Whether the process is run by itself or not, or whether it begins with butynediol or butenediol, the process produces a mixture of 1,4-butanediol and a 2 - alkyl - 1,4 - butanediol. While these can be easily separated by conventional procedures, it may be desirable to keep the mixture intact for it can be cyclized in one step to give a mixture of tetrahydrofuran and a 3 - alkyltetrahydrofuran. A tetrahydrofuran/3 - alkyltetrahydrofuran copolymer can then be prepared directly from this mixture by adding a suitable catalyst and holding the mixture under conditions suitable for copolymerization.
- The process of the invention can be run batchwise, but is more conveniently and preferably run continuously.
- In the continuous mode, a column reactor of appropriate dimensions is packed in the usual manner with a conventional hydrogenation catalyst. Suitable catalysts are, for example, platinum, Raney nickel and cobalt. Raney nickel, especially Raney nickel from which about 25% by weight of aluminum has been removed, is preferred. The catalyst may be in any convenient form, but is ordinarily and preferably granular.
- The butynediol used may be any commercially available type, and may be, for example, that obtained by catalytically reacting acetylene and formaldehyde, using a copper acetylide complex as the catalyst, as described in U.S. Patent 3,560,576 to Kirchner.
- The butenediol, if that is used as a starting material, can likewise be of any commercially available type, and may be, for example, that obtained by the conventional hydrogenation of butynediol.
- The pH value of the butynediol or butenediol is adjusted to the range 8-14, preferably about 10-11, and is then fed continuously through the reaction column.
- The aldehyde, ordinarily as an aqueous solution, is also fed continuously through the column. The aldehyde will be one having the structure shown in equation (1), and will preferably be formaldehyde.
- Enough aldehyde. is fed into the column to provide a diol/aldehyde weight ratio of 2/1 to 200/1, preferably 10/1 to 25/1.
- If the butynediol is obtained by the previously mentioned Kirchner method, it may already contain the proper amount of formaldehyde as an impurity, and separate addition of formaldehyde to the column may be unnecessary.
- Hydrogen is continuously fed into the column, in co-current or countercurrent flow to the other reactants, and is conveniently maintained in the column at a pressure of 6895-55160 kPa (gauge), preferably 34475 kPa (gauge).
- The exit temperature of the reaction mass conveniently is maintained at 10o-200°C, preferably about 140°-150°, by recycling according to well known chemical engineering principles.
- Flow of reactants into the reactor is conveniently regulated to give them a residence time in the reactor of 30-200 minutes, preferably 100-120 minutes.
- The 2 - alkylbutanediol is removed from the column in liquid form, as a mixture with 1,4 - butanediol. The alkylbutandiol can be separated from the 1,4 - butanediol, if one wishes to do this, by fractional distillation conducted according to well known chemical engineering principles.
- The process of the invention, when run in the batch mode, is conducted under basically the same conditions, using the proportions of reactants and the recovery procedures just described.
- Whether run batchwise or continuously, the 2 - alkylbutanediol produced may be catalytically cyclized to a corresponding 3 - alkyltetrahydrofuran, using sulfuric acid as the catalyst, by the general method disclosed in U.S. Patent 3,726,905 to Coates and Reilly. If the product, a mixture of 1,4 - butanediol and 2 - alkyl - 1,4 - butanediol, is kept intact as it comes from the reaction column, both components can be simultaneously cyclized using this method, to give a corresponding mixture of tetrahydrofuran and 3 - alkyltetrahydrofuran.
- This mixture, or one like it made by mixing separate components, can then be copolymerized to form a tetrahydrofuran/3 - alkyltetrahydrofuran copolymer using fluosulfonic acid as the catalyst, as disclosed in U.S. Patent 3,358,042 to Dunlop and Sherman. This copolymer can then be used to prepare a polyurethane by the general method disclosed in U.S. Patent 4,120,850 to Pechhold.
- In the following examples, all parts are by weight.
- Into a fixed-bed column reactor 76 cm long, with an inside diameter of 4.5 cm, were packed 1000 gm of Raney nickel alloy 25% of whose aluminum had been removed with caustic.
- 1,4 - Butynediol, a 50% aqueous solution containing 0.4% of formaldehyde, prepared as shown in U.S. Patent 3,560,576, was brought to pH 11 with sodium hydroxide and then continuously fed into the bottom of the column at a rate of 9 ml per minute.
- Hydrogen was pumped into the bottom of the column and maintained in the column at a pressure of about 34475 kPa (gauge).
- The exit temperature of the product was maintained at about 140°C by recycling.
- The product, a 1/20 mixture of 2 - methyl - 1,4 - butanediol and 1,4 - butanediol, and also containing a small amount of butanol, was removed from the top of the column at a rate of 9 ml per minute.
-
- The slurry was heated to and held at 150°C and a hydrogen pressure of 34475 kPa (gauge), and shaken for one hour.
- The product was a mixture the organic portion of which was composed of 13.2% 2 - methyl - 1,4 - butanediol, 76.7% 1,4 - butanediol, and minor amounts of methanol and butanol.
- Twenty ml of product like that produced in Example 1, and composed of 2.3% of 2 - methyl - 1,4 - butanediol, 42% of 1,4 - butanediol and the remainder water and a small amount of impurities, was distilled until the pot temperature reached 150°C. The residue was cooled to 100°C, and to it was then added 0.25 ml of concentrated sulfuric acid.
- This mixture was heated to 115°C and held there for about 30 minutes, while the product, the organic portion of which contained 8.4% of 3 - methyl - tetrahydrofuran and 91.6% of tetrahydrofuran, distilled off.
-
- The resulting slurry had a pH of 11.9.
- The slurry was heated to and held at 140°C and a hydrogen pressure of 20,684 kPa (gauge) and shaken for 2 hours.
- The product was a mixture the organic portion of which was composed of 10.4% 2 - methyl - 1,4 - butanediol, 73.5% 1,4 - butanediol and minor amounts of methanol and butanol.
Claims (8)
in a butynediol/aldehyde or butenediollalde- hyde weight ratio of 2/1' to 200/1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50231783A | 1983-06-08 | 1983-06-08 | |
US502317 | 1983-06-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0133739A1 EP0133739A1 (en) | 1985-03-06 |
EP0133739B1 true EP0133739B1 (en) | 1986-09-10 |
Family
ID=23997273
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84303842A Expired EP0133739B1 (en) | 1983-06-08 | 1984-06-06 | Process for preparing 2-alkyl-1,4-butanediols |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0133739B1 (en) |
JP (2) | JPS608237A (en) |
BR (1) | BR8402706A (en) |
CA (1) | CA1229342A (en) |
DE (1) | DE3460687D1 (en) |
DK (1) | DK281384A (en) |
MX (1) | MX162211A (en) |
ZA (1) | ZA844264B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7754925B2 (en) | 2005-07-12 | 2010-07-13 | Basf Aktiengesellschaft | Method for the hydrogenation of mass fluxes containing aldehyde |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3502079A1 (en) * | 1985-01-23 | 1986-07-24 | Basf Ag, 6700 Ludwigshafen | METHOD FOR ADDING HYDROGEN AND ORGANIC REMAINS TO OLEFINIC AND ACETYLENICALLY UNSATURATED COMPOUNDS |
US4879420A (en) * | 1988-05-06 | 1989-11-07 | E.I. Du Pont De Nemours And Company | Preparation of mixtures of butanediols |
US4859801A (en) * | 1988-05-26 | 1989-08-22 | E. I. Du Pont De Nemours And Company | Synthesis of mixtures of butanediols |
DE4004884A1 (en) * | 1990-02-16 | 1991-08-22 | Basf Ag | New bis-glycoside(s) from specified diol(s) |
US5618953A (en) * | 1995-02-10 | 1997-04-08 | Mitsubishi Gas Chemical Co., Inc. | Process for producing 3-methyltetrahydrofuran |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3859369A (en) * | 1971-07-26 | 1975-01-07 | Du Pont | Process for the production of 2-methyl-1,4-butanediol |
FR2147161B1 (en) * | 1971-07-26 | 1976-05-14 | Du Pont | |
DE2236036C3 (en) * | 1972-07-22 | 1982-02-04 | Hoechst Ag, 6000 Frankfurt | Diphosphinic acid ester |
JPS5515692A (en) * | 1978-07-12 | 1980-02-02 | Gen Aniline & Film Corp | Excellent raney nickel catalyst and catalytic hydrogenation method of butine diol to butane diol that use said catalyst |
US4153578A (en) * | 1978-07-31 | 1979-05-08 | Gaf Corporation | Catalyst comprising Raney nickel with adsorbed molybdenum compound |
-
1984
- 1984-06-05 BR BR8402706A patent/BR8402706A/en not_active IP Right Cessation
- 1984-06-06 DE DE8484303842T patent/DE3460687D1/en not_active Expired
- 1984-06-06 ZA ZA844264A patent/ZA844264B/en unknown
- 1984-06-06 EP EP84303842A patent/EP0133739B1/en not_active Expired
- 1984-06-07 MX MX201574A patent/MX162211A/en unknown
- 1984-06-07 CA CA000456060A patent/CA1229342A/en not_active Expired
- 1984-06-07 DK DK281384A patent/DK281384A/en not_active Application Discontinuation
- 1984-06-08 JP JP59116792A patent/JPS608237A/en active Granted
-
1992
- 1992-03-10 JP JP4086186A patent/JPH07119220B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7754925B2 (en) | 2005-07-12 | 2010-07-13 | Basf Aktiengesellschaft | Method for the hydrogenation of mass fluxes containing aldehyde |
Also Published As
Publication number | Publication date |
---|---|
EP0133739A1 (en) | 1985-03-06 |
BR8402706A (en) | 1985-05-14 |
JPH0455179B2 (en) | 1992-09-02 |
CA1229342A (en) | 1987-11-17 |
DE3460687D1 (en) | 1986-10-16 |
ZA844264B (en) | 1986-01-29 |
DK281384D0 (en) | 1984-06-07 |
JPS608237A (en) | 1985-01-17 |
JPH07119220B2 (en) | 1995-12-20 |
MX162211A (en) | 1991-04-08 |
JPH05117258A (en) | 1993-05-14 |
DK281384A (en) | 1984-12-09 |
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